Isothiazolazo dyes having coupling components which are free from unsaturated aliphatic radicals

ABSTRACT

Compounds of the general formula I ##STR1## where R is substituted alkyl and K is the radical of a coupling component free from unsaturated aliphatic radicals, are very useful for dyeing cellulose esters and synthetic polyesters.

The present invention relates to compounds of the general formula I ##STR2## where R is substituted alkyl and K is the radical of a coupling component free from unsaturated aliphatic radicals.

R is, in particular, C₁ -C₄ -alkyl which is substituted by chlorine, bromine, cyano, hydroxyl, C₁ -C₄ -alkoxy, phenoxy, C₁ -C₈ -alkoxycarbonyl or unsubstituted or substituted phenyl.

Specific examples of R are 2-chloroethyl, 2-bromoethyl, cyanomethyl, 2-cyanoethyl, 2-hydroxyethyl, 2-methoxyethyl, 2-ethoxyethyl, 2-propoxyethyl, 2-butoxyethyl, 2-phenoxyethyl, methoxycarbonylmethyl, ethoxycarbonylmethyl, 2-methoxycarbonylethyl, 2-ethoxycarbonylethyl, benzyl, phenethyl, o-, m- and p-methylbenzyl, o-, m- and p-bromobenzyl, o-, m- and p-chlorobenzyl, o-, m- and p-methoxybenzyl, o-, m- and p-ethoxybenzyl and o-, m- and p-nitrobenzyl.

The radicals of the coupling components K correspond, for example, to the formula ##STR3## where R¹ is hydrogen, alkyl, aralkyl, or aryl, R² is hydrogen or R³, R³ is unsubstituted or substituted alkyl, aralkyl or aryl, and R⁴ and R⁵ are hydrogen, alkyl, alkoxy, phenoxy, halogen, alkylsulfonylamino, dialkylaminosulfonylamino or acylamino.

Specific examples of R¹, in addition to those mentioned above, are methyl, ethyl, propyl, butyl, benzyl, phenethyl, phenyl, o-, m- and p-tolyl and o-, m- and p-chlorophenyl.

Examples of R³, in addition to those mentioned above, are C₁ -C₆ -alkyl which may be substituted by chlorine, bromine, hydroxyl, C₁ -C₈ -alkoxy, phenoxy, cyano, carboxyl, C₁ -C₈ -alkanoyloxy, benzoyloxy, o-, m- and p-methylbenzoyloxy, o-, m- and p-chlorobenzoyloxy, C₁ -C₄ -alkoxyalkanoyloxy, phenoxyalkanoyloxy, C₁ -C₈ -alkoxycarbonyloxy, C₁ -C₈ -alkoxyalkoxycarbonyloxy, benzyloxycarbonyloxy, phenethyloxycarbonyloxy, phenoxyethoxycarbonyloxy, C₁ -C₈ -alkylaminocarbonyloxy, cyclohexylaminocarbonyloxy, phenylaminocarbonyloxy, C₁ -C₈ -alkoxycarbonyl, C₁ -C₈ -alkoxyalkoxycarbonyl, phenoxycarbonyl, benzyloxycarbonyl or phenethyloxycarbonyl, and further examples are phenyl, benzyl, phenylethyl and cyclohexyl.

Specific examples of R³ are methyl, ethyl, propyl, butyl, phenyl, hexyl, 2-chloroethyl, 2-bromoethyl, 2-cyanoethyl, 2-hydroxyethyl, 2-phenyl-2-hydroxyethyl, 2,3-dihydroxypropyl, 2-hydroxypropyl, 2-hydroxybutyl, 2-hydroxy-3-phenoxypropyl, 2-hydroxy-3-methoxypropyl, 2-hydroxy-3-butoxypropyl, 3-hydroxypropyl, 2-methoxyethyl, 2-ethoxyethyl, 2-propoxyethyl, 2-butoxyethyl, 2-phenoxyethyl, 2-phenoxypropyl, 2-acetoxyethyl, 2-propionyloxyethyl, 2-butyryloxyethyl, 2-isobutyryloxyethyl, 2-methoxymethylcarbonyloxyethyl, 2-ethoxymethylcarbonyloxyethyl, 2-phenoxymethylcarbonyloxyethyl, 2-methoxycarbonyloxyethyl, 2-ethoxycarbonyloxyethyl, 2-propoxycarbonyloxyethyl, 2-butoxycarbonyloxyethyl, 2-phenyloxycarbonyloxyethyl, 2-benzoyloxycarbonylethyl, 2-methoxyethoxycarbonyloxyethyl, 2-ethoxyethoxycarbonyloxyethyl, 2-propoxyethoxycarbonyloxyethyl, 2-butoxyethoxycarbonyloxyethyl, 2-methylaminocarbonyloxyethyl, 2-ethylaminocarbonyloxyethyl, 2-propylaminocarbonyloxyethyl, 2-butylaminocarbonyloxyethyl, 2-methoxycarbonylethyl, 2-ethoxycarbonylethyl, 2-propoxycarbonylethyl, 2-butoxycarbonylethyl, 2-phenoxycarbonylethyl, 2-benzyloxycarbonylethyl, 2-β-phenylethoxycarbonylethyl, 2-methoxyethoxycarbonylethyl, 2-ethoxyethoxycarbonylethyl, 2-propoxyethoxycarbonylethyl, 2-butoxyethoxycarbonylethyl, 2-phenoxyethoxycarbonylethyl and 2-benzoylethyl.

Examples of radicals R4 and R5 are hydrogen, methyl, ethyl, propyl, bromine, chlorine, methoxy, ethoxy, phenoxy, benzyloxy, C₁ -C₆ -alkanoylamino, benzoylamino, C₁ -C₄ -alkylsulfonylamino and di-C₁ -C₄ -alkylaminosulfonylamino.

The compounds of the formula I may be prepared by diazotizing a diazo component of the formula ##STR4## by a conventional method, and then reacting it with a compound of the formula

    H-K.

Details of the reactions may be found in the Examples, wherein parts and percentages are by weight, unless stated otherwise.

The compounds of the formula I range from yellow to blue and are useful for dyeing cellulose triacetate and especially polyesters, on which they give brilliant, deeply colored dyeings having very good fastness characteristics, in particular high lightfastness. In this context, it can be advantageous to use a mixture of compounds of the formula I.

Compounds of particular importance are those of the formula Ia ##STR5## where R⁶ is benzyl, phenethyl, o-, m- or p-chlorobenzyl, o-, m- or p-methoxybenzyl or -ethoxybenzyl or o-, m- or p-nitrobenzyl, R⁷ is hydrogen, methyl, methoxy, ethoxy or chlorine, R⁸ is hydrogen, methyl, methoxy, chlorine, acetylamino, propionylamino, methylsulfonylamino or dimethylaminosulfonylamino, and R² and R³ have the stated meanings.

Preferably, R² is hydrogen or R³, R³ being methyl, ethyl, propyl, butyl, β-cyanoethyl, β-hydroxyethyl, C₁ -C₄ -alkoxycarbonylmethyl, C₁ -C₄ -β-alkoxycarbonyloxyethyl, C₁ -C₄ -alkanoyloxyethyl, C₁ -C₄ -alkoxycarbonyloxyethyl, C₁ -C₄ -alkylaminocarbonyloxyethyl, phenylaminocarbonyloxyethyl, benzyl or phenethyl.

EXAMPLE 1

21.5 parts of 5-amino-3-benzyl-4-cyano-isothiazole were dissolved in 150 parts of a 3:1 glacial acetic acid/propionic acid mixture and 70 parts of 85% strength sulfuric acid, 32 parts of nitrosylsulfuric acid (11.5% of N₂ O₃) were added slowly at 0°-5° C., and the mixture was then stirred for 4 hours at 0°-5° C.

17.4 parts of N-cyanoethyl-N-ethylaniline were introduced into a mixture of 330 parts of water, 35 parts of concentrated hydrochloric acid and 1.7 parts of diisobutylnaphthalene-1-sulfonic acid mixture. About 400 parts of ice were added and the diazo solution was then run in slowly at 0°-5° C. After completion of coupling, the dye suspension obtained was heated to 60° C. and filtered, and the filter cake was washed neutral with water and then dried under reduced pressure at 60° C. 31.5 parts of the dye of the formula ##STR6## were obtained; the product gave very fast bluish red dyeings on polyesters.

EXAMPLE 2

A solution of 25 parts of N-benzyl-N-cyanoethyl-m-toluidine in 100 parts of dimethylformamide was introduced into a mixture of 300 parts of water, 35 parts of concentrated hydrochloric acid and 1.7 parts of diisobutylnaphthalene-1-sulfonic acid mixture. After addition of about 400 parts of ice, a diazo solution prepared as in Example 1 from 21.5 parts of 5-amino-3-benzyl-4-cyano-isothiazole was run in slowly at 0°-5° C. and stirring was continued until coupling was complete. The dye suspension was heated to 50° C. and filtered, and the filter cake was washed neutral with water. Drying under reduced pressure at 60° C. gave 47 parts of the dye of the formula ##STR7## which gave very fast bluish red dyeings on polyesters.

EXAMPLE 3

24.3 parts of 3-methylsulfonylamino-N,N-diethylaniline were dissolved in 150 parts of dimethylformamide, and the solution was added to a mixture of 300 parts of water, 35 parts of concentrated hydrochloric acid and 1.7 parts of diisobutylnaphthalene-1-sulfonic acid mixture. After addition of about 400 parts of ice, a diazo solution prepared as in Example 1 from 21.5 parts of 5-amino-3-benzyl-4-cyano-isothiazole was run in slowly at 0°-5° C. After completion of coupling, the dye suspension was heated to 50° C. and filtered. The filter cake was washed neutral with water and dried under reduced pressure at 50° C. 40.5 parts of the dye of the formula ##STR8## where obtained; the product dyed polyesters in very fast clear reddish violet hues.

EXAMPLE 4

25.0 parts of ethyl-n-propylaminocarbonyloxyethylaniline were dissolved in 20 parts of dimethylformamide and 40 parts of 32 percent strength hydrochloric acid, and the solution was added to a mixture of 300 parts of water and 1.2 parts of diisobutylnaphthalene-1-sulfonic acid mixture. After addition of 400 parts of ice, a solution prepared as in Example 1 from 21.5 parts of 5-amino-3-benzyl-4-cyanoisothiazole was run in slowly at about 0° C. After completion of coupling, the dye was filtered off and washed neutral. Drying under reduced pressure at 50° C. gave 42.4 parts of the dye of the formula ##STR9## which dyed polyesters in very fast clear bluish red hues.

EXAMPLE 5

33.6 parts of cyanoethyl-ethyloxyethyloxycarbonyloxyethylaniline were dissolved in 40 parts of 32% strength hydrochloric acid, and the solution was added to a mixture of 300 parts of water and 1.2 parts of diisobutylnaphthalene-1-sulfonic acid mixture. After addition of 400 parts of ice, a solution prepared as in Example 1 from 21.5 parts of 5-amino-3-benzyl-4-cyanoisothiazole was slowly added dropwise, with the temperature not exceeding 0° C. After completion of coupling, the dye formed was filtered off with suction and washed neutral. Drying under reduced pressure at 50° C. gave 47 parts of the dye of the formula ##STR10## which dyed polyesters in very fast clear red hues.

The dyes identified by their diazo component and coupling component in the Table which follows were obtained in a similar manner.

    __________________________________________________________________________     DNNK                                                                           Example                                        Hue on                          No.  D                 K                       polyesters                      __________________________________________________________________________           ##STR11##                                                                                        ##STR12##              red                               7  "                                                                                                 ##STR13##              red                               8  "                                                                                                 ##STR14##              bluish red                        9  "                                                                                                 ##STR15##              bluish red                        10 "                                                                                                 ##STR16##              bluish red                        11 "                                                                                                 ##STR17##              bluish red                        12 "                                                                                                 ##STR18##              bluish red                        13 "                                                                                                 ##STR19##              bluish red                        14 "                                                                                                 ##STR20##              red                               15 "                                                                                                 ##STR21##              red                               16 "                                                                                                 ##STR22##              red                               17 "                                                                                                 ##STR23##              bluish red                        18 "                                                                                                 ##STR24##              violet                            19 "                                                                                                 ##STR25##              bluish violet                     20 "                                                                                                 ##STR26##              reddish violet                    21 "                                                                                                 ##STR27##              red                               22 "                                                                                                 ##STR28##              bluish red                        23 "                                                                                                 ##STR29##              bluish red                        24 "                                                                                                 ##STR30##              bluish red                        25 "                                                                                                 ##STR31##              red                               26 "                                                                                                 ##STR32##              reddish blue                      27 "                                                                                                 ##STR33##              red                               28 "                                                                                                 ##STR34##              red                               29 "                                                                                                 ##STR35##              red                               30 "                                                                                                 ##STR36##              bluish red                        31 "                                                                                                 ##STR37##              yellow                            32 "                                                                                                 ##STR38##              yellow                            33 "                                                                                                 ##STR39##              orange                            34 "                                                                                                 ##STR40##              bluish red                        35 "                                                                                                 ##STR41##              red                               36 "                                                                                                 ##STR42##              red                               37 "                                                                                                 ##STR43##              bluish red                        38 "                                                                                                 ##STR44##              bluish red                        39 "                                                                                                 ##STR45##              bluish red                        40 "                                                                                                 ##STR46##              red                               41 "                                                                                                 ##STR47##              violet                            42 "                                                                                                 ##STR48##              red                               43 "                                                                                                 ##STR49##              bluish red                        44 "                                                                                                 ##STR50##              bluish red                        45 "                                                                                                 ##STR51##              bluish red                        46 "                                                                                                 ##STR52##              red                               47 "                                                                                                 ##STR53##              violet                            48 "                                                                                                 ##STR54##              red                               49 "                                                                                                 ##STR55##              red                               50 "                                                                                                 ##STR56##              red                               51 "                                                                                                 ##STR57##              bluish red                        52 "                                                                                                 ##STR58##              violet                            53 "                                                                                                 ##STR59##              bluish red                        54 "                                                                                                 ##STR60##              violet                            55 "                                                                                                 ##STR61##              violet                            56 "                                                                                                 ##STR62##              violet                            57 "                                                                                                 ##STR63##              bluish red                        58 "                                                                                                 ##STR64##              bluish red                        59 "                                                                                                 ##STR65##              red                               60 "                                                                                                 ##STR66##              red                               61 "                                                                                                 ##STR67##              red                               62 "                                                                                                 ##STR68##              red                               63 "                                                                                                 ##STR69##              red                               64 "                                                                                                 ##STR70##              red                               65                                                                                 ##STR71##                                                                                        ##STR72##              bluish red                        66 "                                                                                                 ##STR73##              bluish red                        67 "                                                                                                 ##STR74##              bluish red                        68 "                                                                                                 ##STR75##              bluish red                        69 "                                                                                                 ##STR76##              bluish red                        70 "                                                                                                 ##STR77##              red                               71 "                                                                                                 ##STR78##              bluish red                        72 "                                                                                                 ##STR79##              bluish red                        73 "                                                                                                 ##STR80##              red                               74 "                                                                                                 ##STR81##              bluish red                        75 "                                                                                                 ##STR82##              bluish red                        76 "                                                                                                 ##STR83##              red                               77 "                                                                                                 ##STR84##              bluish red                        78 "                                                                                                 ##STR85##              bluish red                      __________________________________________________________________________ 

We claim:
 1. An isothiazolazo dye of the formula: ##STR86## wherein R is a C₁ -C₄ alkyl which is substituted by chlorine, bromine, cyano, hydroxyl, C₁ -C₄ -alkoxy, phenoxy, C₁ -C₈ -alkoxycarbonyl or an unsubstituted phenyl or a phenyl substituted by methyl, chloro, bromo, methoxy, ethoxy or nitro; and K is ##STR87## wherein R¹ is hydrogen, alkyl, aralkyl, aryl or aryl substituted by chlorine, R² is hydrogen or R³, R³ is C₁ -C₆ alkyl or C₁ -C₆ alkyl substituted by chlorine, bromine or hydroxyl, C₁ -C₈ alkoxy, phenoxy, cyano, carboxyl, C₁ -C₈ -alkanoyloxy, benzoyloxy, o-, m-, and p-methylbenzoyloxy, o-, m- and p-chlorobenzoyloxy, C₁ -C₄ -alkoxyalkanoyloxy, phenoxyalkanoyloxy, C₁ -C₈ -alkoxycarbonyloxy, C₁ -C₈ -alkoxyalkoxycarbonyloxy, benzyloxycarbonyloxy, phenethyloxycarbonyloxy, phenoxyethoxycarbonyloxy, C₁ -C₈ -alkylaminocarbonyloxy, cyclohexylaminocarbonyloxy, phenylaminocarbonyloxy, C₁ -C₈ -alkoxycarbonyl, C₁ -C₈ -alkoxyalkoxycarbonyl, phenoxycarbonyl, benzyloxycarbonyl or phenethyloxycarbonyl, or phenyl, benzyl, phenylethyl and cyclohexyl; and R⁴ and R⁵ are hydrogen, alkyl, alkoxy, phenoxy, halogen, alkylsulfonylamino, dialkylaminosulfonylamino or acylamino.
 2. The isothiazolazo dye as claimed in claim 1, wherein R³ is methyl, ethyl, propyl, butyl, phenyl, hexyl, 2-chloroethyl, 2-bromoethyl, 2-cyanoethyl, 2-hydroxyethyl, 2-phenyl-2-hydroxyethyl, 2,3-dihydroxypropyl, 2-hydroxypropyl, 2-hydroxybutyl, 2-hydroxy-3-phenoxyproyl, 2-hydroxy-3-methoxypropyl, 2-hydroxy-3-butoxypropyl, 3-hydroxypropyl, 2-methoxyethyl, 2-ethoxyethyl, 2-propoxyethyl, 2-butoxyethyl, 2-phenoxyethyl, 2-phenoxypropyl, 2-acetoxyethyl, 2-propionyloxyethyl, 2-butyryloxyethyl, 2-isobutyryloxyethyl, 2-methoxymethylcarbonyloxyethyl, 2-ethoxymethylcarbonyloxyethyl, 2-phenoxymethylcarbonyloxyethyl, 2-methoxycarbonyloxyethyl, 2-ethoxycarbonyloxyethyl, 2-propoxycarbonyloxyethyl, 2-butyoxycarbonyloxyethyl, 2-phenyloxycarbonyloxyethyl, 2-benzoyloxycarbonyloxyethyl, 2-methoxyethoxycarbonyloxyethyl, 2-ethoxyethoxycarbonyloxyethyl, 2-propoxyethoxycarbonyloxyethyl, 2-butoxyethoxycarbonyloxyethyl, 2-methylaminocarbonyloxyethyl, 2-ethylaminocarbonyloxyethyl, 2-propylaminocarbonyloxyethyl, 2-butylaminocarbonyloxyethyl, 2-methoxycarbonylethyl, 2-ethoxycarbonylethyl, 2-propoxycarbonylethyl, 2-butoxycarbonylethyl, 2-phenoxycarbonylethyl, 2-benzyloxycarbonylethyl, 2-β-phenylethoxycarbonylethyl, 2-methoxyethoxycarbonylethyl, 2-ethoxyethoxycarbonylethyl, 2-propoxyethoxycarbonylether, 2-butoxyethoxycarbonylethyl, 2-phenoxyethoxycarbonylethyl and 2-benzoylethyl; and R⁴ and R⁵ are hydrogen, methyl, ethyl, propyl, bromine, chlorine, methoxy, ethoxy, phenoxy, benzyloxy, C₁ -C₆ -alkanoylamino, benzoylamino, C₁ -C₄ -alkylsulfonylamino and di-C₁ -C₄ -alkylaminosulfonylamino.
 3. The isothiazolazo dye as claimed in claim 1 having the formula: ##STR88## wherein R⁶ is benzyl, phenethyl, o-, m- or p-chlorobenzyl, o-, m- or p-methoxybenzyl or -ethoxybenzyl or o-, m- or p-nitrobenzyl; R⁷ is hydrogen, methyl, methoxy, ethoxy or chlorine; R⁸ is hydrogen, methyl, methoxy, ethoxy, chlorine, acetylamino, propylamino, methylsulfonylamino, or dimethylaminosulfonamino; and R² and R³ have the stated meanings.
 4. The isothiazolazo dye as claimed in claim 3, wherein R² is hydrogen or R³, R³ being being methyl, ethyl, propyl, butyl, β-cyanoethyl, β-hydroxyethyl, C₁ -C₄ -alkoxycarbonylmethyl, C₁ -C₄ -β-alkoxycarbonyloxyethyl, C₁ -C₄ -alkanoyloxyethyl, C₁ -C₄ -alkoxycarbonyloxyethyl, C₁ -C₄ -alkylaminocarbonyloxyethyl, phenylaminocarbonyloxyethyl, benzyl or phenethyl.
 5. An isothiazolazo dye having the formula: ##STR89##
 6. An isothiazolazo dye having the formula: ##STR90##
 7. An isothiazolazo dye having the formula: ##STR91##
 8. An isothiazolazo dye having the formula: ##STR92##
 9. An isothiazlazo dye having the formula: ##STR93## 